JPS604197B2 - Method for producing organotin trihalide - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to the production of certain novel organotin dihalides that are particularly useful in producing organotin stabilizers for polyvinyl chloride or other polymers.

The formation of tin-carbon bonds is a necessary step in the synthesis of organotin compounds. Known methods for forming such bonds are the Grignard process by Reaction Skin 4 M & 1 - R 4 Sn + side and 12 where R is alkyl or substituted alkyl.

Different methods are reaction $NC14'R3AI→3R4Sn
+4AIC13 aluminum alkyl process.

The third method is the WArtz process SnC144RCI+mother Na→R4Sn+mother NaCI.

In these methods, the R4Sn obtained is RSmHa13,
It is useful as a starting material for the production of R2SnHa12 and R3SNHal (wherein 1 represents a halogen atom).

Although the above reactions are quantitative in nature, these methods are unattractive because they endanger those attempting them. Moreover, unlike the production of alkylorganotin compounds, the production of functionally substituted organotin compounds by these processes is not straightforward. Other less hazardous processes, such as direct production by the reaction Sn+2RHal→R2SmHa12, give low yields with Sn ratios of 12, producing by-products such as R3S al and RS a13.

Reaction SdHa120RHal→RSOHa13 by carbon-
Insertion of stannous halides into halogen bonds requires catalysts and high temperatures, and yields are poor.

Equation R2SnH2 12R'-CH=C ratio → R2Sn(C ratio-
The addition of organotin hydrides to unsaturated hydrocarbons with CH2-R')2 must be considered only an academic method, in which the production of organotin hydrides itself is both expensive and dangerous.

The present invention provides an industrially attractive and non-hazardous process for producing functionally substituted organotin halides.

In the method of the present invention, the following substances 'a' stannous halide, {b} hydrogen halide and (C} (wherein R, .R2, R3 and R4 are hydrogen atoms, alkyl groups) in a polar solvent are used. , represents a carboxylic acid group, ester group, aldehyde group, acid halide group or ketone group, provided that R, and R
olefins of the type (at least one of which contains a carbonyl group adjacent to a carbon-carbon double bond) are reacted with each other, and then the reaction product having the formula is removed from the medium. It is characterized by

Generally, the halide may be a chloride, bromide, diodide or fluoride, although chloride is usually preferred for reasons of cost and optimum yield.

In order for the reaction between the olefin and other reactants to proceed, the olefin must be activated, i.e. R,
It is considered essential that at least one of , R2, R3, or R4 contains an active luponyl group adjacent to the olefin double bond.

Examples of suitable olefins for use in the process of the invention are methyl acrylate methyl acrylate crotonate mesityl chloride acryloyl methyl pinyl ketone.

Thus, the active carbonyl group may be part of an acid group, ester group, aldehyde group, or may be a ketone group. The starting material is preferably an alkyl ether, such as diethyl ether, in a solvent at ambient temperature (1
oo to 30oo) with each other to form the desired compound.

For olefins with one active group and no external substituents, the reaction is almost quantitative. for example,
The use of methyl acrylate with stannous chloride and hydrogen chloride provides the desired organotin compound in a yield of 98% based on tin.

The new organotin compounds prepared in accordance with this invention can be made into very useful organotin stabilizers for polyvinyl chloride and other polymers by any of the established techniques for stabilizer production.

Such preparation usually involves reaction with organic fatty acids having 6 to 18 carbon atoms, partial esters of maleic acid, alkylthiols or mercaptoesters. Thus, we thus obtain novel organotin salts with the general formula RS, in which R represents an organic group of the starting trihalide compound and x is an organic acid residue obtained in the main reaction with an acid or mercabutane. .

In particular, the organic residue x is selected from the group consisting of -S(C ratio)nCOOalkyl, -S alkyl, -OCOalkyl, and -OCOCH=CHCOOalkyl, where n is 1 or 2. The organotin dihalides produced according to the invention themselves have certain stabilizing effects on polymers, and also find use as catalysts in the production of polyurethane foams and silicone resins, or in esterification reactions.

However, their primary use is now recognized as intermediates in the production of the novel organotin salts of the formula RSail 3 identified above.

These new salts make excellent components of stabilizer compositions for polymers, especially polyvinyl chloride. Their stabilizing performance is completely equal to, if not better than, that of conventional butyltin compounds. Also, their toxicity is generally on the lower side, whereas sulfur-containing salts are often much less toxic. The following examples serve to illustrate the invention.
Example 1 In a 500' three-necked flask equipped with a stirrer, thermometer, countercurrent condenser and gas inlet tube and placed in an ice/salt cooling tank, 80 g of anhydrous stannous chloride and 36.3 g of methyl acrylate were added. 150 tons of dimethoxychetane was charged as a solvent and a polar solvent.

To the stirred solution was added 36 m of hydrogen chloride gas over a period of 2 hours, maintaining the temperature at 2°C. After this time, the solvent was removed in a flash evaporator and the residue was extracted with Toluene 100. The resulting extract was vacuum distilled at 100° C. and 4-side Hg pressure to leave a pale colored residue, which was cooled and crystallized. Elemental analysis and infrared spectroscopy showed that the melting point was 70qo and the boiling point was 174 qo.
00 (4 skin Hg), composition cH3o8-CWC day 2Sn
It was found that the product C13 was obtained in 89% yield based on tin. Example 2 In the same equipment and following the same process as used in Example 1, anhydrous SnC 1270 and ethyl acrylate 37.9
and 30 g of hydrogen chloride gas (added over 1/2 hour) were reacted in Jetyl Ether 140, maintaining the temperature between 15° and 20° C.

The solvent was removed on a rotary evaporator and the residue was extracted with 100 g of toluene. Toluene and other volatiles were removed from the extract by distillation below 10000/4 willow Hg pressure.

It was found that the residue (95°C) crystallized on cooling and consisted primarily of a total melting point of <RTIgt;

The yield was 79% based on tin. Examples 3-7 These examples relate to similar preparations carried out in the same manner on the equipment described in Example 1, starting with different olefins and using other solvents.

The results are summarized in Table A. Table A *Product contains impurities and is difficult to characterize.

Examples 8-11 In the experiments below, dry hydrogen chloride gas was first passed through the solution, followed by gradual addition of the activated olefin.

The results are summarized in Table B. Table B * The product contains impurities, making it difficult to characterize it.

** In this example, SnC was
The reaction was carried out at 12,500 ml, 800 ml of diethyl ether, 153 ml of HCI gas, and 335 ml of methyl acrylate.

Reference Example 1 In this Reference Example and the following Reference Example, the product obtained in Example 11 was used as P.I. V. C. The applicability of the organotin compounds according to the invention is demonstrated using them as starting materials for the production of stabilizers.

In this reference example, 31.0% was placed in a 3-necked flask equipped with a stirrer, a thermometer, and a backflow cooling system.
NaOH dissolved in 8 ml of water and then 100 ml of water
12 minutes were added and stirring continued at 40°C for 15 minutes.

Then 62.4 g of isooctyl thioglycolate was added and the temperature was raised to 89C in 30 minutes. The butanol layer was then separated from the aqueous phase, and the butanol was removed from the butanol layer by evaporation to leave a colorless liquid (quantitative yield based on 82% tin). The product after hot furnace filtration was identified by analysis.

This compound '11' is a solid P. V.C. It was shown that thermal stability comparable to that obtained with monobutyltin tris (isooctyl thioglycolate), which is commonly used in Moreover, the compound (1) was sufficiently substituted for the usual dibutyltinbis(isooctyl thioglycolate) in the production of P.V.C. bottles at a level of 1%.Reference Example 2 A method similar to the above Reference Example 31.2 parts of organotin halide dissolved in 110 parts of butanol was first added to 1 part of water.
It was treated with a solution of 16.0% sodium carbonate and then 62.0% lauryl mercaptan.

After separating the butanol layer and removing the solvent, a colorless liquid was obtained in quantitative yield based on tin. The product was identified as.

The performance of this compound ■ was then evaluated against the common stabilizer monobutyltintris (lauryl mercaptide) in a PVC bottle formulation consisting of PVCIO Ikarito, 1 part ester lubricant, and 1 part stabilizer, parts by weight. However, the performance of this compound (1) appeared to be completely equivalent to that of a conventional stabilizer.

Claims (1)

[Claims] 1 The following substances (a) stannous halide, (b) hydrogen halide, and (c) ▲Mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1, R_2 , R_3 and R_4 represent a hydrogen atom, an alkyl group, a carboxylic acid group, an ester group, an aldehyde group, an acetic acid halide group, or a ketone group, provided that R_
1 and R_2 shall contain a carbonyl group adjacent to a carbon-carbon double bond) type olefins, react with each other, then the formula ▲ mathematical formula, chemical formula, table, etc. ▼ A method for producing an organotin trihalide, which comprises isolating a reaction product having ▼ from a medium.